Materials for ammonia synthesis

ABSTRACT

Disclosed herein are doped perovskite oxides. The doped perovskite oxides may be used as a cathode material in an electrochemical cell to electrochemically generate ammonia from N 2 . The doped perovskite oxides may be combined with nitride compounds, for instance iron nitride, to further increase the efficiency of the ammonia production.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application 62/791,968, filed on Jan. 14, 2019, the entire contents of which are hereby incorporated in its entirety.

STATEMENT OF GOVERNMENT SUPPORT

This invention was made with government support under Grant no. CHE-1213443 awarded by the National Science Foundation. The government has certain rights in the invention.

FIELD OF THE INVENTION

The application relates to perovskite oxide compositions useful as catalysts for the synthesis of ammonia from nitrogen gas and water. The compositions can further be combined with nitride compounds to enhance the efficiency of the process.

BACKGROUND

Ammonia (NH₃) is an important industrial chemical, and a critical component in fertilizer production. Historically, the Haber-Bosch process has been used for large scale ammonia production. This process converts nitrogen and hydrogen gas to ammonia according to the reaction N₂+3H₂→2NH₃. Although the overall efficiency of the process is good, the process requires high pressures and hydrogen gas, which is typically sourced from fossil fuels.

Electrocatalytic processes, which can be conducted at atmospheric pressures, and in which hydrogen is sources from water, is an appealing alternative to the Haber-Bosch process. Generally, water and nitrogen gas are combined at a cathode to product ammonia and oxide anion (O²⁻), and the oxide anion is converted to oxygen gas at the anode. Typically, the cathode material catalyzes the formation of ammonia from water and nitrogen. There are several different electrocatalytic modalities known, include liquid electrolyte cells, molten salt electrolytes, composite membranes, and solid-state electrolytes. The later is especially attractive due to the enhanced reaction rate compared with liquid electrolytes.

Several features are important for a successful solid-state electrocatalytic reactor: (i) the cathode/catalyst material should possess high electrical conductivity; (ii) the material should possess high oxide anion conductivity; (ii) the material should have high thermal stability; and (iii) the material should have a suitable thermal expansion coefficient.

There remains a need for improved methods for manufacturing ammonia from cheap and abundant feedstocks. There remains a need for materials having the aforementioned constellation of attributes beneficial for electrochemical production of ammonia. There remains a need for improved electrochemical cells for the production of ammonia.

SUMMARY OF THE INVENTION

Disclosed herein are perovskite oxides having high electrical conductivity, high oxide anion conductivity, high thermal stability and suitable thermal expansion coefficients. The perovskite oxides are useful as cathode materials in a wide variety of different electrochemical cells, including solid-state electrochemical cells for the electrocatalytic production of ammonia. The perovskite oxides can be combined with one or more additional active materials to further enhance the electrochemical production of ammonia. Suitable active materials include transition metal nitrides, including iron nitride.

The details of one or more embodiments are set forth in the description below. Other features, objects, and advantages will be apparent from the description and from the claims.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1A depicts x-ray diffraction analysis for several doped perovskite oxides, showing the presence of an orthorhombic phase. FIG. 1B depicts an enlarged view of the encircled peaks in FIG. 1A. The splitting and broadening of the encircled peaks signifies the presence of a rhombohedral phase along with the orthorhombic phase in La_(0.7)Sr_(0.2)Co_(0.2)Fe_(0.8)O₃.

FIG. 2 depicts the electrical conductivity for several doped perovskite oxides as a function of temperature.

FIG. 3 depicts a process schematic for the production of a button cell.

FIG. 4 depicts a process schematic for the electocatalytic production of ammonia.

FIG. 5A depicts rate for the electrocatalytic production of hydrogen gas with several doped perovskite oxides. FIG. 5B depicts the Faradaic efficiency (defined as the fraction of H⁺ that reacts with N₂ to form ammonia) for several doped perovskite oxide. FIG. 5C depicts the ammonia production rate at different currents for La_(0.7)Sr_(0.2)Co_(0.2)Fe_(0.8)O₃. For water electrolysis, a 3% H₂O in helium feed composition was used, at a temperature of 600° C., at 1 atm. For ammonia production, a 3% H₂O in nitrogen gas feed composition was used, at a temperature of 600° C., at 1 atm.

FIG. 6 depicts a schematic for the production of Fe₃N from Fe₂O₃ nanopowder. The resulting product has a hexagonal crystal structure with six iron and 2 nitrogen atoms in the unit cell.

FIG. 7 depicts x-ray diffraction analysis for Fe₃N prepared using the apparatus depicts in FIG. 6 . The synthesis was conducted at 500° C. for 4 hours, 450° C. for 2.5 hours, 400° C. for 45 minutes, 400° C. for four hours, and 400° C. for 45 minutes. The analysis shows that the product prepared at 450° C. for 2.5 hours does not include any Fe₂O₃ or Fe⁰ phase.

FIG. 8 depicts the results of surface etching of Fe₃N with an argon ion gun.

FIG. 9 depicts the nitrogen released by temperature-programmed decomposition of Fe₃N. Integration of the mass spectrometry signal for nitrogen indicates that Fe₃N prepared at 450° C. for 2.5 hours exhibited the greatest N₂ release.

FIG. 10 depicts the mobility and accessibility of lattice nitrogen in Fe₃N prepared at 450° C. for 2.5 hours. The material was heated at a rate of 10° C./min in a 5% H₂/He environment, resulting in the reaction with H₂ to form ammonia at atmospheric pressure.

FIG. 11 depicts the ammonia production rate using La_(0.7)Sr_(0.2)Co_(0.2)Fe_(0.8)O₃ promoted by Fe₃N.

DETAILED DESCRIPTION

Before the present methods and systems are disclosed and described, it is to be understood that the methods and systems are not limited to specific synthetic methods, specific components, or to particular compositions. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

As used in the specification and the appended claims, the singular forms “a,” “an” and “the” include plural referents unless the context clearly dictates otherwise. Ranges may be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, another embodiment includes-, from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another embodiment. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

“Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

Throughout the description and claims of this specification, the word “comprise” and variations of the word, such as “comprising” and “comprises,” means “including but not limited to,” and is not intended to exclude, for example, other additives, components, integers or steps. “Exemplary” means “an example of” and is not intended to convey an indication of a preferred or ideal embodiment. “Such as” is not used in a restrictive sense, but for explanatory purposes.

Disclosed are components that can be used to perform the disclosed methods and systems. These and other components are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these components are disclosed that while specific reference of each various individual and collective combinations and permutation of these may not be explicitly disclosed, each is specifically contemplated and described herein, for all methods and systems. This applies to all aspects of this application including, but not limited to, steps in disclosed methods. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with any specific embodiment or combination of embodiments of the disclosed methods.

Disclosed herein are perovskite oxides useful as cathode materials in electrochemical cells, including cells for the electrocatalytic production of ammonia. The electrochemical production of ammonia involves the following steps.

-   -   (a) electrochemically reducing H₂O and N₂ at a cathode to         provide NH₃ and O₂ ₋ ; and     -   (b) oxidizing the O₂ ₋ to give oxygen gas.

The perovskite oxides disclosed herein have the general structure ABO₃, wherein the A metal is typically an alkaline earth metal or rare earth element and the B metal is a transition metal, preferably iron. The ionic and electroconductivity of perovskites can be modified by doping the material either at the A-site or B-site. Preferred dopants at the A-site include lanthanide metals such as La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu. In general, it is preferred that the doping metals are aliovalent with the A and B metals, e.g., that they have different valencies.

In certain embodiments, the doped perovskite can be a compound of Formula (I):

A¹ _(w)A² _(x)X_(y)Fe_(z)O₃  [Formula (I)],

-   -   wherein:     -   A¹ is a lanthanide;     -   A² is an alkaline earth metal;     -   X is one or more metals in the +1 or +2 oxidation state;     -   w is from 0.5-1.0;     -   x is from 0-0.5;     -   y is from 0-0.5; and     -   z is from 0.5 to less than 1.0;     -   wherein w, x, y, and z are chosen to maintain electroneutrality.

Suitable A¹ lanthanides include La, Tb, Gd, Sm, Pr, and Nd, and suitable A² alkaline earth metals include Sr, Mg, Ca, and Ba.

Suitable X metals include Ni, Co, Ti, Mn, Zn, Cu, Li, Al, Sc, V, Cr, Ga, Ge, Y, Zr, Nb, In, V, W, Mb, Pd, Pt, Ag, Au, Cd, and combinations thereof.

In certain embodiments, A¹ can be lanthanum, e.g., a compound of Formula (II):

La_(w)A² _(x)X_(y)Fe_(z)O₃  [Formula (II)],

wherein A², X, w, x, y and z are as defined above.

In some embodiments, A² can be strontium, e.g., a compound of Formula (III):

A¹ _(w)Sr_(x)X_(y)Fe_(z)O₃  [Formula (III)],

wherein A¹, X, w, x, y and z are as defined above.

In certain preferred embodiments, A¹ can be lanthanum and A² can be strontium, e.g., a compound of Formula (IV):

La_(w)Sr_(x)X_(y)Fe_(z)O₃  [Formula (IV)],

wherein X, w, x, y and z are as defined above.

For any of the compounds of Formula (I), (II), (III), and (IV), X can be absent (e.g., y=0). For embodiments in which y is not 0, preferred X metals include Co and Ni.

For any of the compounds of Formula (I), (II), (III), and (IV):

-   -   w can be from 0.5-1.0; 0.5-0.9; 0.5-0.8; 0.5-0.7; 0.5-0.6;         0.6-1.0; 0.6-0.9; 0.6-0.8; 0.6-0.7; 0.65-0.75; 0.75-0.85; or         0.55-0.65;     -   x can be from 0-0.5; 0.05-0.5; 0.1-0.5; 0.15-0.5; 0.2-0.5;         0.25-0.5; 0.3-0.5, 0.35-0.5; 0.05-0.1; 0.05-0.15; 0.1-0.2;         0.15-0.25; 0.2-0.3; 0.25-0.35; 0.3-0.4; 0.35-0.45; or 0.4-0.5.     -   y can be from 0-0.5; 0.05-0.5; 0.1-0.5; 0.15-0.5; 0.2-0.5;         0.25-0.5; 0.3-0.5; 0.35-0.5; 0.05-0.1; 0.05-0.15; 0.1-0.2;         0.15-0.25; 0.2-0.3; 0.25-0.35; 0.3-0.4; 0.35-0.45; or 0.4-0.5;         and     -   z can be from 0.5 to less than 1.0; 0.5-0.9; 0.5-0.8; 0.5-0.7;         0.5-0.6; 0.6-1.0; 0.6-0.9; 0.6-0.8; 0.6-0.7; 0.65-0.75;         0.75-0.85; or 0.55-0.65.

In preferred embodiments, w is from 0.6 to 0.8, x is from 0.15 to 0.25, y is from 0.15 to 0.25, and z is from 0.5 to less than 1. In such implementations, A¹ can be La, A² can an alkali earth metal, including Be, Mg, Ca, Sr, or Ba, and X is Co or Ni.

The doped perovskite oxides can be obtained by a sol-gel or co-precipitation process. In a preferred implementation, a solution of A¹, A², X, and Fe salts in relative molar concentrations corresponding to the molar concentration of the final perovskite oxide can be converted to a gel and then calcined to give the perovskite oxide. Nitrate salts are particularly convenient, but other counterions may be used as known in the art. The solution is combined with a chelating agent (e.g., EDTA and/or citric acid) and/or a polyol (e.g., ethylene glycol) under pH control to form a gel, which is then dried and later calcined to the give the perovskite oxide.

In certain implementations, one or more doped perovskite oxides can be further combined with one or more nitride compounds having the formula M_(a)N_(b), wherein M can be Fe, Mb, Co, Cr, or V (preferably Fe), a can be 1, 2, 3, or 4, and b can be 1, 2, 3, or 4. The weight ratio of the perovskite oxide(s) to nitride compound(s) can be from 10:1 to 1:10, from 5:1 to 1:5, from 1:2 to 2:1, from 1:1 to 10:1, from 1:1 to 5:1, from 1:1 to 3:1, from 1:1 to 1:10, from 1:1 to 1:5, or from 1:1 to 1:3. The nitride compounds, prior to combination with the perovskite oxide compounds, can be substantially free of oxides (e.g., M_(a′)O_(b′), wherein a′ and b′ are selected to maintain electroneutrality) and can be substantially free of the reduced metal M⁰. As used herein, substantially free can mean no more than 10%, no more than 5%, no more than 1%, or no detectable (by x-ray diffraction) of any the above described impurities.

The doped perovskite oxides, either alone or in combination with one or more nitride compounds, can be used as a cathode material in an electrochemical cell. The doped perovskite oxides and nitride compounds can be crystalline, amorphous, or a mixture thereof. Generally, the electrochemical cell is a solid oxide electrolyte cell. The electrochemical cells can be used for the production of numerous useful materials, including hydrogen gas, water, and especially ammonia. In such implementations, nitrogen gas and water feedstocks are electrochemically converted to oxygen and ammonia. The ammonia may be captured using conventional techniques, including reaction with an aqueous acid to trap the material as an ammonium salt. Thus, in some implementations, the electrochemical cell can include a cathode as described here, in ionic communication with an anode, with a proton-conductive electrolyte disposed between the cathode and anode. The electrochemical cell may be in fluid communication with one or more feedstocks, for instance water, air, or nitrogen gas. In some embodiments, the feedstock can be a combination of water, air, and/or nitrogen gas. As used herein, nitrogen gas refers to a feedstock having a higher concentration of nitrogen relative to the amount of nitrogen naturally found in air. The electrochemical cell can also be in fluid communication with an ammonia trap, for instance an aqueous acid or an acidic resin.

A variety of suitable anodes can be used in the electrochemical cells disclosed herein. In some instances, the anode can palladium, platinum, silver, gold, yttria stabilized zirconia, lanthanum strontium manganate, or a combination thereof. The anode can further include at least one doped fluorite oxide, for instance yttria stabilized zirconia, GDC, and ABO₃-type perovskite oxides where A is selected from alkaline earth metals and lanthanoids and B is one or more transition metals.

A variety of suitable electrolytes can be used in the electrochemical cells disclosed herein. In some instances the electrolyte can be a solid electrolyte, for instance yttria stabilized zirconia (YSZ), scandia stabilized zirconia (ScSZ), gadolinium doped ceria (GDC), perovskite-type oxides such as lanthanum strontium gallium magnesium oxide (LSGM), lanthanum yttrium germanate (LaYGe), or a combination thereof. Other electrolytes include barium-zirconium-cerium-yttrium oxides, composites of CsH₂PO₄ and SiP₂O₇, and barium-certium-yttrium oxide. The perovskite oxide(s) (with or without nitride compound) can be printed as a slurry on a surface of the electrolyte and then fired at high temperature (a similar process can be employed for the anodic component). The electrodes can then be affixed to a conductor and placed in electrical communication with power supply. In some implementations, the electrochemical cell can have the general features depicted in FIG. 4 .

The power supply can be configured to provide a voltage between the cathode and anode. The power supply can be configured to provide a current in an amount from 0.1-50 mA, from 0.1-25 mA, from 0.1-10 mA, from 0.1-5 mA, from 0.1-2.5 mA, from 0.1-100 A, from 0.5-100 A, from 1-100 A, from 5-100 A, from 10-100 A, from 25-100 A, from 50-100 A, from 0.1-50 A, from 0.5-50 A, from 1-50 A, from 5-50 A, from 10-50 A, or from 25-50 A.

The compositions and methods of the appended claims are not limited in scope by the specific compositions and methods described herein, which are intended as illustrations of a few aspects of the claims and any compositions and methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative compositions and method steps disclosed herein are specifically described, other combinations of the compositions and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein or less, however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated. The term “comprising” and variations thereof as used herein is used synonymously with the term “including” and variations thereof and are open, non-limiting terms. Although the terms “comprising” and “including” have been used herein to describe various embodiments, the terms “consisting essentially of” and “consisting of” can be used in place of “comprising” and “including” to provide for more specific embodiments of the invention and are also disclosed. Other than in the examples, or where otherwise noted, all numbers expressing quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood at the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, to be construed in light of the number of significant digits and ordinary rounding approaches. 

1-18. (canceled)
 19. A method of generating ammonia, comprising: electrochemically reducing H₂O and N₂ with a composition comprising a perovskite oxide, to provide NH₃ and O₂ ₋ ; and oxidizing the O₂ ₁ to give oxygen gas, wherein the perovskite oxide has the formula: A¹ _(w)A² _(x)X_(y)Fe_(z)O₃, wherein: A¹ is selected from La, Tb, Gd, Sm, Pr, and Nd; A² is selected from Sr, Mg, Ca, and Ba; X is one or more metals in the +1 or +2 oxidation state; w is from 0.5-1.0; x is from 0-0.5; y is from 0-0.5; and z is from 0.5 to less than 1.0; wherein w, x, y, and z are chosen to maintain electroneutrality.
 20. The method of claim 19, wherein the electrochemical reduction is performed by supplying an electric current to the perovskite oxide of claim 1, wherein the current applied is in an amount from 0.1-50 mA.
 21. The method of claim 19, wherein X is Ni, Co, Ti, Mn, Zn, Cu, Li, Al, Sc, V, Cr, Ga, Ge, Y, Zr, Nb, In, V, W, Mb, Pd, Pt, Ag, Au, Cd, or a combination thereof.
 22. The method of claim 19, wherein A¹ is La.
 23. The method of claim 19, wherein A² is Sr.
 24. The method of claim 19, wherein w is from 0.6 to 0.9.
 25. The method of claim 19, wherein z is from 0.6 to 0.9.
 26. The method of claim 19, wherein X is Ni or Co.
 27. The method of claim 19, wherein x is from 0.15 to 0.25.
 28. The method of claim 19, wherein y is from 0.15 to 0.25.
 29. The method of claim 19, wherein the composition further comprises one or more nitride compounds having the formula M_(a)N_(b), wherein M is selected from Fe, Mb, Co, Cr, and V, a is selected from 1, 2, 3, or and 4, and b is selected from 1, 2, 3, and
 4. 30. The method of claim 29, wherein M is Fe.
 31. The method of claim 29, wherein the weight ratio of perovskite oxide to nitride compound is from 10:1 to 1:10. 